Process for dyeing acid-modified nylon with biscationic azo dyes

ABSTRACT

Orange to violet biscationic azo dyes having the formula   WHERE R1 alkyl R2 alkyl or hydroxyalkyl R3 alkyl, hydroxyalkyl or benzyl OR R2 and R3 together alicyclic ring OR R1, R2, and R3 together pyridinium ring R4 H or Cl W 1,4-naphthylene or   R5 and R6 H, alkyl, alkoxy or Cl R7 H, alkyl, alkoxy, Cl, NHCO alkyl or NHCOC6H5 R8 H, Cl, alkyl or alkoxy   Y N R9R2R3 or NHCOCH2N R9R2R3, where R9 R1 or H m 0 or 1 N 0 OR 1 Z H when n O and OH when n 1 A anion AND WHERE ALKYL GROUPS CONTAIN 1-4 CARBON ATOMS, ARE PARTICULARLY WELL SUITED FOR DYEING OF BULK CONTINUOUS FILAMENT (BCF) nylon styling carpet, and have good exhaust and lightfastness on acid-modified nylon and excellent reserve on unmodified nylons, at the preferred dyeing pH range of 6-6.5. The dyes are prepared by coupling p-aminophenacylammonium or p-(paminophenylazo)phenacylammonium salts to N,N-disubstituted anilines containing a pendant tertiary amine or quaternary ammonium group attached to the nitrogen atom.

United States Patent 1191 James [451 Sept. 2, 1975 PROCESS FOR DYEING ACID-MODIFIED NYLON WITH BISCATIONIC AZO DYES [75] Inventor: Daniel Shaw James, Hockessin, Del.

[73] Assignee: E. I. Du Pont de Nemours and Company, Wilmington, Del.

22 Filed: May 16,1973

21 App1.No.: 356,908

Related US. Application Data [62] Division of Ser. No. 58,707, July 27, 1970, Pat. No.

Primary Examiner-Floyd D. Higel 5 7] ABSTRACT Orange to violet biscationic azo dyes having the formula R alkyl or hydroxyalkyl R alkyl, hydroxyalkyl or benzyl or R and R together alicyclic ring or R R and R together pyridinium ring R, H or Cl W 1,4-naphthylene or R and R H, alkyl, alkoxy or Cl R 1-1, alkyl, alkoxy, Cl, NHCO alkyl or NHCOC H R H, C1, alkyl or alkoxy 69 alkyl alky x= -N N or N 0 alkyl Y N 11512 11,, or NHCQCHZNGB 11,11,12 where Z=Hwhenn=OandOHwhenn=1 A= anion and where alkyl groups contain 1-4 carbon atoms, are particularly well suited for dyeing of bulk continuous filament (BCF) nylon Styling carpet, and have good exhaust and light-fastness on acid-modified nylon and excellent reserve on unmodified nylons, at the preferred dyeing pH range of 6-6.5. The dyes are prepared by coupling p-aminophenacylammonium or p- (p-aminophenylazo)phenacylammonium salts to N,N- disubstituted anilines containing a pendant tertiary amine or quaternary ammonium group attached to the nitrogen atom.

2 Claims, No Drawings This is a division, of application Ser. No. 58,707, filed July 27, 1970 now U.S. Pat. No. 3,759,893.

BACKGROUND OF THE INVENTION Multicolored bulked continuous filament (BCF) nylon styling carpeting has grown rapidly in popularity since its introduction a few years ago. Such carpeting initially contained several polyamide modifications which differ from each other with respect to the concentration of free amine end groups in the fiber. U.S. Pat. No. 3,078,248 describes the preparation of polyamide fibers of varying amine end content. Since amine groups act as dye sites for acid dyes, these modified nylons vary in acid dye receptivity. Hence, when a carpet composed of three such nylons having low, medium and high amine end content (which may be termed light, mediumand deep-dyeable nylon, respectively) is dyed with a suitable acid dye or dyes, a threetone effect is produced. Greater versatility of shade is obtainable by using disperse dyes in addition to acid dyes. Disperse dyes are not site-dyeing (since they possess no ionic groups) and thus dye all nylon modifications of the kind described above to the same depth, ir-

respective of the amineend concentration. To illustrate this point, one can visualize a tricomponent nylon carpet dyed first with a suitable red acid dye and then with a yellow disperse dye. The red dye will produce light, medium and deep red shades, respectively, on the three different kinds of nylon. the yellow disperse dye, however, will dye all three nylons to the same depth of shade. The resulting shades will be reddish-yellow, orange and scarlet, respectively.

With the introduction of acid-modified nylons (e.g. as in U.S. Pat. No. 3,184,436), the range of multicolored effects obtainable on BCF nylon styling carpeting was greatly increased. Acid-modified nylons, which contain sulfonic acid groups on the polymer chain, are dyeable with cationic dyes but have little affinity for acid dyes. Thus, a carpet-containing two or three nylo'ns of varying affinity for acid dyes 'and an acidmodified nylon which reserves (is not stained by) acid dyes can be dyed at will with any combination of shades, including primary colors (those colors that cannot be obtained by mixing other colors together) side by side on the same carpet. Dyeing methods have been developed so that such carpets can be dyed with acid and cationic dyes in a single dyeing operation. Thus, a red cationic dye and a blue acid dye (with a suitable dyebath additive to prevent coprecipitation of the dyes) will produce varying shades of blue on the acidreceptive nylons and a red shade on the acid-modified cationic dye-receptive nylon.

The choice of cationic dyes for acid-modified nylon in styling carpeting depends on two main considerations, namely, a high degree of fastness (particularly to light) on the acid-modified nylon and a lack of staining on the unmodified nylo ns. The former consideration is self-explanatory since the fastness requirements for carpet dyes are higher than for almost any other dye end-use; the latter consideration is important since cross-stains can have poor fastness properties and would tend to dull the shade of the acid dyes on the unmodified nylon components and minimize the color contrast between the different types of fiber.

It has been found that thestaining of unmodified nylon with cationic dyes depends on the pH at which the dyes are applied to the substrate. Many commercial, monocationic dyes have satisfactory non-staining characteristics on unmodified nylon at low pH (i.e. 4 or below). However, at'the preferred dyeing pH range for monocationic dyes of 66.5, staining becomes more apparent and, in most cases, tends to become unacceptable for commercial use.

SUMMARY OF THE INVENTION Nylon styling yarns containing acid-modified nylon and unmodified nylon fibers can be dyed in an aqueous dyebath at a pH of from about 6 to about 6.5 with novel orange to violet biscationic azo dyes having the formula where R alkyl R alkyl or hydroxyalkyl R alkyl, hydroxyalkyl or benzyl or R and R together alicyclic ring or R R and R together pyridinium ring R H or C] W 1,4 -naphthylene or R and R H, alkyl, alkoxy or Cl R H, alkyl, alkoxy, Cl, NHCO alkyl or NHCOC H R H, Cl, alkyl or alkoxy and where alkyl groups contain 1-4 atoms. The dyes have excellent reserve of non-acid-modified nylon, deep dyeing characteristics on acid-modified nylon and excellent exhaust from the dyebath.

DESCRIPTION OF THE INVENTION The monoazo dyes of this invention may be prepared by conventional techniques, by diazotizing a monoquaternary diamine of the formula (where R R and R are as defined above) in aqueous hydrochloric acid at about O-lOC. with sodium nitrite and coupling the resulting diazonium compound to a quaternary amine or a tertiary amine salt of the structure (where the symbols are as defined above). The coupling reaction may be carried out by dissolving the coupler in water at room temperature or below, but preferably at about 20C., and then slowly adding the diazonium salt preparation to it, or vice versa. To increase the reaction rate, the pH of the reaction mixture may be raised to about 34 by adding a suitable inorganic salt or base, such as an alkali metal acetate, carbonate, bicarbonate or hydroxide. Sodium acetate and sodium hydroxide are the preferred agents.

The disazo dyes of this invention may be prepared by coupling the diazo compound, obtained as described above, to a-naphthylamine or an amine of the formula (where R and R are as defined above. Table 1 lists examples of such amines.

Table l aniline 0- or m-toluidene 0- or m-ethylaniline 0- or m-anisidine 0- or m-phenetidine 0- or m-chloroaniline cresidine 2,5-xylidine 2,5-dimethoxyaniline 2,5-diethoxyaniline S-chloro-o-toluidine S-chloro-o-anisidine Coupling may be effected at room temperature or below, but preferably at l0l5C., by dissolving the amine totally or partially in aqueous acid and then slowly adding the diazonium salt preparation to the coupler preparation, or vice versa. Adjustment of the pH as described above may be carried out to increase the rate of coupling.

The monoazo amine thus obtained may be diazotized, at room temperature or below, in situ or after first isolating and redissolving or reslurrying the intermediate in aqueous hydrochloric acid. It is then coupled to the final coupler as described above.

The monoazo and disazo dyes thus prepared may be salted from solution if necessary and then isolated by filtration.

Monoand disazo dyes in which the coupler is the salt of a tertiary amine may be used in this form, or may be quatemized by any of the agents known for this purpose in the art. Common examples include alkyl chlorides, bromides and iodides, benzyl chloride, bromide and sulfate, alkyl sulfates and alkyl p-toluenesulfonates. Alkyl may contain up to four carbon atoms, but methyl and ethyl are the preferred species.

Another alternative procedure for preparing the subject dyes is by diazotizing p-aminophenacyl chloride or 4-amino-3-chlorophenacyl chloride and coupling as described above to give monoor disazo intermediates. These compounds may then be treated with a tertiary amine to give the desired products.

For economic reasons, the preferred anion is chloride. However, substitution of other anions in no way impairs the desirable properties of the subject dyes and in some cases (i.el for ease of isolation of the dye) may be beneficial. Various procedures are available for introducing other anions. For instance, salts such as zinc chloride, sodium iodide, sodium fluoborate, etc, may

be used as salting agents to precipitate the biscationic dyes as the zinc chloride double salt, the iodide and the fluoborate, respectively. Hydrochloric acid may be replaced with sulfuric acid in the procedures described above to produce the sulfate form of the dyes. Quaternization of the coupler compounds, before or after dye formation, may be effected by any of the agents known in the art for this purpose. Thus may such anions as bromide, methosulfate and p-toluenesulfonate be introduced. Picrate and phosphate are two more potentially desirable anions.

The preparation of the starting monoquaternary diamines is described in US. Pat. No. 2,821,526. Acetanilide is reacted with chloroacetyl chloride in the presence of aluminum chloride to give pacetamidophenacyl chloride. Reaction of this material with a suitable tertiary amine, followed by removal of the N-acetyl group by acid hydrolysis, produces the desired monoquaternary amine. Examples of such diamines are given in Table 2.

Table 2 (p-aminophenacyl)trimethylammonium chloride (p-aminophenacyl)triethylammonium chloride (p-aminophenacyl)tri-n-propylammonium chloride (p-aminophenacyl)tri-n-butylammonium chloride (p-aminophenacyl )dimethyl )2-hydroxyethyl )ammonium chloride (p-aminophenacyl )diethyl( 2-hydroxyethyl )ammonium chloride (p-aminophenacyl )ethylbis( 2-hydr0xyethyl )ammonium chloride 5; (p-aminophenacyl)methylbis(hydroxyisopropyl)ammonium chloride (p-aminophenacyl )benzyldimethylammonium: chloride (p-aminophenacyl)benzylmethyl(2-hydroxyethyl)amor tertiary amine; by reaction with ethylene oxide, re-

placement ofth' resulting hydroxyl group with chlorine and subsequent reaction with a secondary or tertiary amine; reaction with epichlorhydn'n and then a secondary or tertiary amine; reaction with epichlorhydrin, replacement of the terminal chlorine atom with a primary amine group'and then sequential reaction with from N-alkylanilines or m-chloro, m-alkyl or m-alkoxy derivatives thereof, e.g. by sequential reaction with ethyleneimine, chloroacetyl chloride and a secondary OCH 'chloroacetyl chloride and a secondary or tertiary amine a'nd so on. Other useful couplers are prepared by-alkylating and quaternizing N-phenylpiperazine, 0r

.them-chlforo, m-alkyl or m-alkoxy derivatives thereof,

with any of the known quatemizing agents, examples of which are given above. Examples of such couplers are given in. Table 3.

Table 3 The biscationic azo dyes of this invention have been found to have good exhaust and lightfastness on-acidmodified BCF nylon fibers. Such polymersfare described, for instance, in US. Pat. No. 3,184,436 and contain sulfonate groups along the polymer chain which act as dye sites for basic'orcationic dyes. The instant dyes have also been found to displayan almost total lack of affinity for unmodified nylon fibers under neutral to weakly acidic conditions. In other words, at pH 6-6.5, the biscationic dyes almost completely reserve nylon fibers which do not contain sulfonate groups.- This behavior differs from that of known monocationic orange and red dyes, which tend to stain unmodified nylon under near-neutral conditions and which display good reserveonly under more acidic conditions (i.e. pH 4 or below).

The importance of these observations lies in the fact that nylon styling carpeting, which contains acidmodified and unmodified nylons, is piece-dyed most satisfactorily at pH 6-6.5. Acid and cationic dyes are applied to the carpeting from a single dyebath, which contains an additive to prevent coprecipitation of the oppositely charged dye molecules. There are several reasons why neutral to weakly acidic conditions are preferred for this dyeing procedure.

a. Although cationic dyes generally reserve unmodified nylons more efficiently at lower pH, they do not exhaust as well from the dyebath onto acid-modified nylon.

b. Acid dyes generally exhaust more efficiently at lower pH, but suffer a decrease in levelness on unmodified nylon and tend to stain acid-modified nylon.

c. Styling carpet that has a jute backing undergoes increased staining of the nylon, by impurities in the jute, with increasing acidity, causing dulling of dye shade and deterioration of dye fastness properties.

At neutral to weakly acidic conditions, cationic dyes may be applied to nylon styling carpet in conjunction with neutral-dyeing acid dyes, which have satisfactory exhaust and levelness under these conditions. It has now been discovered that the biscationic dyes described hereinabove have significantly better nonstaining properties on unmodified nylon at pH 6-6.5 than anyknown commercial orange to red cationic dye.

Although biscationic dyes have been disclosed in the patent literature for several years for use on various substrates, particularly for acid-modified acrylic fibers, biscationic dyes like those disclosed in the present invention were found to have very limited utility on acrylics (such as those disclosed in US. Pat. No. 2,837,500 and US. Pat. No. 2,837,501 because of low affinity and poor buildup on the substrates. Much the same thing was found to be true of acid-modified polyester (such as is disclosed in US. Pat. No."3, l8,272 Thus, it was totally unexpected to find that the biscationic dyes of this invention have entirely adequate buildup on acid-modified nylon, producing deep orange to ,violet shades thereon.

Commercial nylon styling carpet usually contains acidmodified nylon and from two to four unmodified nylons of varying acid dye receptivity which are tufted onto a backing in a random pattern'to give the desired styling effects. The acid dye receptivity of the unmodified nylon fibers is a function of their amineend content, which may range from to morethan 100.- gramequivalents of free amine ends per 10 grams of polymer. Four unmodified nylon fibersinthe same styling yarn may 'havethe following amine-end content:

1. 5-25 gram-equivalents light-dyeable" with acid' dyes 2." 25-55 gram-equivalents medium-dyeable with acid dyes "3. 55-100 gram-equivalents acid dyes 4. 100-120 gram-equivalents with acid dyes The deep-dyeing nylons (3) and (4) are disclosed in US. Pat. No. 3,078,248.

The carpeting can be dyed with acid and cationic dyes in the same dyebath by using as a dyeing assistant a sulfobetaine of the generalstructure ultradeep-dyeable where R aliphatic hydrocarbon radical of 7-17 carbon atoms The preparation of these compounds is described in US. Pat. No. 3,280,179. Their utility in this particular end-use is disclosed in the defensive publication of Robbins dated 4-29-69, Ser. No. 634,477. The functions of the sulfobetaine additive are to prevent coprecipitation of the acid and cationic dyes, to enhance the levelness of both classes of dye without suppressing buildup and to minimize cross-staining.

Piece dyeing is carried out at temperatures above C. and preferably near the boil (-l00C.). Lower temperatures cause inferior exhaust and poor contrast through cross-staining. The pH of the dyebath may be anywhere from 3 to 9, but the most favored pH range is 66.5, for reasons given earlier in the discussion.

The sulfobetaine dyeing assistant may be used in amounts as low as 0.05% of the weight of the fiber being dyed, but the best results are obtained with 02-03%. Amounts in excess of 0.5% of the weight of the fiber have led to an increase in cross-staining.

The dyeing procedure is advantageously preceded by a bleach scour, as described in Example 17 (a), in.

. formed by customary means.

The aforementioned dyeing procedure may be adapted for the continuous dyeing of styling carpet, a comparatively new technique which is referred to'in Melliand Textilberichte," 48, 415-448 (April, '1967).

deep-dyeable with Continuous dyeing is taught as being related to piece dyeing in that it is an aqueous process, but

a. at very low bath ratios, i.e. :1 instead of 30:1 to 50:1, and

b. the rate of fixation is much faster, since temperatures near the boil are attained more quickly in a steamer than in heating up a beck. Cationic and acid or direct dyes may also be printed onto nylon styling carpeting, with excellent results.

Although the discussion has been devoted up to this point to styling carpeting, there are other areas in which BCF nylon styling yarns may be effectively used, such as upholstery and accent or throw rugs. The dyeing of these items may be carried out by the same means as that described for carpeting, using suitable equipment. Thus, carpeting is usually dyed in becks; upholstery is usually dyed in jigs; accent or throw rugs are usually dyed in paddle machines.

In order to evaluate the instant biscationic dyes for use on nylon styling yarns, they were dyed singly and in the absence of any acid dyes, onto a skein of acidmodified, 1300 denier BCF nylon (such as is described in US. Pat. No. 3,184,436) in the presence of a skein of light-dyeable, unmodified, 3700 denier BCF nylon having an amine-end content of 5-25 gramequivalents per grams of polymer. The dyeing procedure was the same as that described in Example 17 and the evaluation of cross-staining and light-fastness for some typical dyes of this invention appears in Example 20.

EXAMPLES The preparation of the dyes of this invention may be illustrated by the following examples. Parts are given by weight.

EXAMPLE 1 Coupling of (p-Aminophenacyl)trimethylammonium Chloride (Quatamine) to [2-( N-ethyl-m-toluidino )ethylcarbamoylmethyl trimethylammonium Chloride A solution of 22.9 parts of Quatamine in 250 parts of water and 35 parts of 10 N-hydrochloric acid was cooled to 510C. and treated with 23.5 parts of 5N- sodium nitrite solution. After stirring at this temperature for a /2 hour, excess nitrous acid was destroyed with a small quantity of sulfamic acid. The diazo preparation was added over a period of minutes to a solution of 32.9 parts of the coupler in 100 parts of water at 10l 5C., containing enough acetic acid to give the solution a pH of 5.0. As coupling proceeded, the pH was maintained at 3.5-4.0 by intermittent addition of sodium acetate. The reaction mixture was stirred for 2 hours at 10-15C., after which the temperature was allowed to rise to room temperature. The solution was then heated to 50-60C. and parts of sodium iodide were added in portions. Precipitation of the dye occurred.

The temperature was allowed to fall to room temper-' ature and the reaction mass was stirred at this temperature overnight. The solids were isolated by filtration, washed with 500 parts of 10% sodium iodide and then with 500 parts of isopropanol and dried. The chromatographically pure, reddish-orange powder had an absorptivity of 42.5 liters gram cm. at 490 mp. (in dimethylacetamide water 4 1).

Found: C, 43.8, 43.6; H, 5.7, 5.8; Azo N, 3.9, 4.0; I. 35.2, 35.0. Calc. for C H N O I C, 44.1; H, 5.7; Azo

On the basis of the above results, the structure of the dye is 625 c a mucocu ntcmf) EXAMPLE 2 I Coupling of (p-aminophenacyl)pyridinium Chloride to the Coupler of Example 1 In the procedure of Example 1, 22.9 parts of Quatamine were replaced by 24.9 parts of (p- EXAMPLE 3 Coupling of Quatamine to N-ethyl-N-(m-tolyl )-N ',N'-diethyl-2-hydroxy- 1 ,3- propylenediamine 15.1 Parts of Quatamine were diazotized in a conventional manner, essentially as described in Example .13 14 l. The diazonium salt solution was added to a suspenprocedure described in Example 1. 72 Parts of the cousion of 18.5 parts of coupler in 25 parts of water ad- 'plerwere then added at -l0C. and the reaction mixjusted to pH 5 with acetic acid. and cooled at 5 C. ture stirred at this temperature for 1 hour. The temper- The pH was maintained at about 5 during the coupling ature was then allowed to rise to 25C. over a perprocedure by addition of sodium acetate. The reaction 5 iod of 2 hours. The pH of the reaction mass was admixture was then stirred for /2 hour and then warmed justed to 3-4 with sodium acetate and 26 parts of soto 30C. The product was salted out of solution by dium fluoborate were added. The reaction mass was the addition of 23 parts of sodium iodide, isolated by stirred for 2 A2 hours and the solids were isolated by filfiltration, washed with 5% sodium iodide solution and tration, washed with 250 parts of 10% sodium fluobothen with a little water, and dried. The dark red powder 10 rate and then with 120 parts of isopropanol and finally had an absorptivity of 48.5 liters gram cm? at 495 dried. Yield: 44 parts of red needles, having an absorpmp.. tivity of 53.0 liters gramcm.- at 489 mu. Based on the above procedure the structure of the" Based on the above procedure, the structure of dye is the dye is 2 l I on i e c 3 CHgCiH-Crig 4(CH EXAMPLE 4 EXAMPLE-6 Quaternization of the Dye of Example 3 Coupling of A mixture of 15 parts of the dye of Example 3, l7 (p'amfnophenafyl)dlmethyuz'hydrggethylg' 3 parts of methyl iodide, 4.6 parts of potassium carbon-. ammomum chlonde the coupler o Xamp e ate and 200 parts of isopropanol was heated to the re- 0 Dia ti ati f 15,5 parts f flux temperature with stirring for 6 hours. An addiaminophenacyl)dimethyl-(2-hydroxyethyl)ammonium tional l 1.5 parts of methyl iodide was then added and chloride was carried out essentially as described in Exthe reaction mixture stirred at the reflux temperature a le 1, for a further 4 hours. After allowing the mass to cool T th di i lt l ti was dd d 17 2 bystirring overnight, the product was S parat d y filof the pure coupler of Example 3 over a 15-20 minutes tration, washed with isopropanol and dri d. h ye period. The reaction mixture was stirred at l0l5C. had an absorptivity of 28.5 liters gram cm." at 488 for 2 hours and then allowed to warm to room temperamu. ture. After stirring for a further 2 hours, 30% sodium Based on the above procedure, the truc r Of the hydroxide solution was added to raise the pH to 4 and dye is the temperature raised to 50-55C. Addition of 25 EXAMPLE '5 parts of sodium fluoroborate caused the dye to precipitate as an oil, which crystallized on stirring the reaction mass overnight at room temperature.

The solids were isolated by filtration, restirred in parts of 20% sodium fluoroborate solution, reisolated,

20.4 Parts of Quatta r i Were diaZOtiZed y the washed with 10% sodium fluoroborate solution and Coupling of Quatamine to [3-( N-ethyl-m-toluidino )-2-hydroxypropyl]trimethylammonium chloride driedv The chromatographically pure-orange powder partS'10f5%'Sali solution andfinally with 100 parts of had an absorptivity of 44.4 liters gram (rm-. a 38 isopropanol After being dried, the redpowder was mp Based On the above Procedure the structure O found to have an absorptivity of 6815 liters gram cm dye is I at 488 mg. The structure of. the intermediate is:

CH3 1 .z

V 1 CH CH CH-GH' N (C H 3 CH3 1 t1) 6H 2.

EXAMPLE 7 QCll Coupling of (p-aminophenacyl)pyridinium Chloride to 69 /T- N phenyl-N,N-dimethylpiperazinium Iodide 2O (cnfiyecugco g 5 f) I NHZ A solution of 7 parts of (p- I I aminophenacyl)pyridinium chloride in 75 parts of H water and 7 parts of ION-hydrochloric acid were 6) 3 treated with 7.3 parts of SN-sodium nitrite at O5C.

After stirring the reaction mixture for a /2 hour, excess 25 b, The second part of the diazo preparation was nitrous acid was estroyed with ulfamic i The treated with 15.2 parts of 2,5-dimethoxyaniline, essendiazo preparation was added to a mixture of 9.2 parts tially as described in (a) above. The resulting brown the p r and 100 Parts Of Water, the mixture powder hadan absorptivity of 62.5 liters gram cm. being first adjusted to pH 4 with acetic acid and cooled t 490 m in to lOC. Sodium acetate as added during the cou- 30 Th t u t of the intermediate is:

pling reaction to maintain the pH of the reaction mix- 3 ture at 4 -4.5. The mixture was stirred for 1 V2 hours 3 y at ca. C. and then overnight at room temperature. y

The solids were isolated by filtration and washed with (CH3) 3 CHZCO NN 2 parts of water and then 50 parts of isopropanol. The

OCT-I3 dark brown dye was slurried in parts of isopropanol, isolated by filtration, washed with isopropanol and dried. The chromatographically pure tinctorially weak c. The third' portion of the 'diazo preparation was dye had a shoulder at 360 mu, where the absorptivity treated with 12 parts of m-toluidine, as described in (a) was 19.6 liters gram cm V Based on the above procedure the structure of the ity of 703 liters gram crnf at' 454 mg. The structure dye is of the intermediate is (Where A is cl and/ or 1 A I 6) EXAMPLE 8 C CO@" "Ni-l Coupling of Quatamine to (a) cresidine (b) C18 C 2,5-dimethoxyaniline (c) m-toluidine n3 Diazotization of 68.5 parts of Quatamine was carried out as in Example 1. The resulting solution of the diazonium salt was divided into three equal parts. EXAMPLE 9 a. To the first part was added a partial solution of 13.6 parts of cresidine in 50 parts of water containing Coupling of the Monoazo Intermediates of Example 8 to N'N-Diethyl-N-ethyl-N-(m-tolyl)ethylenediamine enough acetic acid to dissolve about half of the cresi- Diazotization of 165 parts of the intermediate dine. The reaction mixture was stirred at l0-.-l5C. for f Example 8 a) was ff t d i aqueous h d 4 hours and then overnight at roomtemperature. Filric acidyat 1 1'5C usingla 25% molar excess of nation yielded Solids which w washed, i 200 Parts dium nitrite. After 1 /2 hours, excess nitrous acid was of 20% salt solution, 200 parts of 10% salt solution, 200 destroyed with Smfamic'apid:

f. 40 above. The resulting orange powder had an absorptive- C e (CH NC H COi N=N, Nell j N g g; 21

' I V g I C2ll4N (C2115); C 3 C 3 i I l v Coupling was effected by addition of 9.2 parts of the 10 EXAMPLE l 2 pure coupler to the diazonium salt solution at l0l5C. The reaction mixture was stirred at this temperature for 3 hours and then at room temperature Quantemlzanon ofthe Dye of Example 9 (c) overnight. Quaternization of parts of the dye of Example 9 The pH of the reaction mass was then adjusted to 5.0 (c) .with 21.5 parts .of methyl iodide, using the procewith caustic soda solution. 11.5 Parts of sodium dure of Example 4, produced a dark reddish-brown iodide were added and the mass was heated to powder having an absorptivity of 43.3 liters gram 45C. and then-stirred at room temperature overcm. at 510 mu. Based on the above procedure, the night. structure at the dye is:

G) 2 a T CH CH H Filtration yielded solids which were reslurried in 200 EXAMPLE 1 1 parts of 1% sodium iodide solution. The dye wasreisolated by filtration, washed with parts of 1% sodium Preparation of iodide, reslurried in 50 parts of isopropanol, reisolated, 3 l-Amino-3-chlorophenacyl)trimethylammonium washed with 50 parts of isopropanol and dried. The Chloride (o-Chloroquatarnine.) red-brown powder had an absorptivity of 35.0 liters I gram cm. at 525 mu. 1

Based on the above procedure, the dye has the struc- A solution of 18.75 parts of pracetylaminophenacyl ture: I r chloride in 140 parts of acetic acid and 32.5 parts of OCH a. m-Chloro-p-acetylaminophenacyl Chloride CH3 CH b. Diazotization and coupling of 17.2 parts of the concentrated hydrochloric acid was cooled to 05C. monoazo intef'mediate of 1 1 8 t P A solution of 4.4 parts of sodium chlorate in 10 parts formed esennany as descnbed (a) above f f of water was added dropwise and allowed to react at .a dark, olive-green powder having an absorptivity of room temperature for three hours. The product was 60.5 liters gram cm. at 563 mu. t

Based on the above procedure, the structure f h isolated by filtration and washed with blsulfite solution dye is: r and then with water. It was then recrystallized from an 001-1 .9 jif 41 2 5 6. I (011 x011 00 'N=N 4 6+.) 21

. I v g i J 2 c. The procedure of Example 9-(a),- using the mono-1 acetone-water mixture. to yield 9.7 parts of product,

azo intermediate of pl 1) d m.p. 1s2-1s4; ir.(Nujol) 3,400 (N-H) and 1,690 havi an abso t 't of 43.0 l't s F t 11 y cm. c =o). Anal. Calcd for C, l-l Cl NO (246): 0,

Based on the above procedure the structure .of'the H, 5 Folmdl 49-1, H, dye is: 3.9, 4.0; CI, 28.3, 28.4; N, 5.8, 5.8.

b. (4-Acety1amino-3-ch1orophenacyl )trimethylammonium Chloride c. o-Chloroquatamine" 11.1 Parts of (4-acetylamino-3-chlorophenacyl)- trimethylammonium chloride were heated in 90 parts of water and 81 parts of concentrated hydrochloric acid at reflux. The aqueous reaction solution had 5.12% diazotizable compound by weight (100% yield).

EXAMPLE 12 2O Coupling of o-Chloroquatamine to [2-( N-ethylanilino )ethyl ]trimethylammonium Chloride Diazotization of 13.2 parts of o-chloroquatamine was effected by a conventional procedure. The diazo solution was added to a solution of 12.5 parts of the coupler in 60 parts of water at 510C. The pH was adjusted to 44.5 with sodium acetate, as required. After stirring for /2 hour, the temperature was allowed to rise and the reaction mixture was stirred at room temperature for 1 hour- It wasthen warmed to C. and 25 parts of sodium fluoroborate were slowly added. Precipitation of the dye started immediately.

After stirring overnight, the solids were isolated by filtration, washed with 5% sodium fluoroborate solution, then with isopropanol, and dried. The dye had an absorptivity of 52.1 liters gram cm. at 478 mp. Found: C, 46.5, 46.4; H, 5.8, 5.8; N, 11.0, 11.0; Azo N, 4.6, 4.6. Calcd for C H B ClF N O: "C, 46.6; H, 5.9; N, 11.4; Azo N, 4.5.

The structure of the dye is:

and coupling to 18.9 parts of coupler were carried out essentially as described in Example 12. The dye had an absorptivity of 47.5 liters gramcm. at 490 mp.. Found: C, 48.1, 48.0; H, 6.1, 6.1; N, 10.4, 10.3; Azo N, 4.4, 4.3. Calcd for C H B CIF N O: C, 49.5; H, 6.4; N, 10.7; Azo N, 4.3. The dye has the structure:

EXAMPLE 14 Coupling of o-Chloroquatamine to N-ethyl-N-(rn-tolyl )-N',N'-diethyl-2-hydroxy-l ,3-

propylenediamine Diazotization of 13.2 parts of o-chloroquatamine and coupling to 13.7 parts of coupler was carried out essentially as described in Example 12, except that acetic acid was also added to dissolve the coupler prior to addition of the diazo compound. The dye was salted from solution with sodium chloride. The dye had an absorptivity of 58.2 liters gram cm.'l16 1 at 513 mu. Found: C, 52.3, 52.6; H, 6.9, 6.9; N, 11.1, 11.2; Azo N, 4.8, 5.0. Calcd for C l-l Cl N O C, 55.7; H, 7.1; N, 12.5; Azo N, 5.0. The dye has the structure:

Coupling of Quatamine to [2-( N-ethyl-mtoluidino )ethyl diethylmethylammonium methosulfate lent amount of N-ethyl-N-( m-tolyl )-N ,N diethylethylenediamine. The product was precipitated (CH (fiat r from solution with sodium chloride, isolated by filtration, reslurried in 100 parts of water for 1 hour and reisolated by filtration. The solids were washed in turn with 5% and then 1% sodium chloride solution i I and dried. Yield: 14.5 parts. The dye had an absorptivity of 59.9 liters gram cm. at 570 mu. Based on the N N 2 5 P) I i?) above procedure, the structure of the dye is N (C ll i cu ll 3 CH3 (01+: am s N=N N:

The dyes of Examples l-7, 9, l0'and 12-16 were ap- 15 plied to.

EXAMPLE 16 Preparation of Two Dyes from 0 11 p-(4-aminonaphthylazo)phenacylammonium Chloride 20 N N 2C A mixture of 41.9 parts of p-(4-aminonaphthylazo)- C2HLLN(C2H5)2 phenacylammonium chloride, 300 parts of water, 50 I parts of acetic acid and l 1.6 parts of lON-hydrochloric H acid was cooled to 20C. and 34.2 parts of SN-sodium. nitrite were slowly added. After stirring for minutes at excess nitrite was destroyed with a small The following examples illustrate the dyeing methods quantity of sulfamic acid. The diazonium salt -solution f0r banded test carp prepared as d ib d on page was cooled to and divided into two equal parts- 15 above. In order to demonstrate the reserve of the a. To one half of the diazo solution was added a solu- 30 bi i i d on difi d l th e d d ion f 1 14 p s of N- yl-N-p ylin the absence of acid dyes onto the banded nylon cardiethylethylenediamine in 25 Parts of watef'and 1O peting. The carpeting contained acid-modified, mediparts of acetic acid. After stirring at 15C. for 2 hours, d b1 d l -d -d bl BC]: nylon fithe reaction mixture was allowed to warm Up to room' berg tufted in a random pattern on a non-woven polytemperature over a l-hour period. The pH was adjusted propylene b ki to 32:05 with sodium acetate and the mass was heated to 4045C. with stirring. A solution of 10.8 EXAMPLE 17 parts of sodium iodide in 150 parts of water was added Dyeing of Banded BCFNylon Carpeting and the mixture stirred overnight. The mother-liquor was then decanted and the oily dye was triturated in. 40 v 250 parts of 1% sodium iodide solution. The resulting 100 Parts of the carpetmg descnbed above were a. Bleach Scour slurry was then heated at 30-40C. for 1 hour and the heated for 5 minutes at E in 4000 Parts of water solids isolated by filtration and dried. Yield: 25.5 parts. containing The dye had an absorptivity of 30.9 liters gram cm. sodium perborate 4 parts t 545 m trisodium phosphate 0.25 part a a sulfobetaine* 0.5 part Based on the above procedure, the structure of the dye is @/CllzClly OH i (CH %cn co--N=N N= 5 3 2 where R C alkyl 30%) C18 C mono-unsaturated 40%).

The temperature was raised to 160F. for 15 minutes N 2 5 Q and the carpet rinsed in water at 100F. N

\ a b. Dyeing Procedure C H A C H 2 4 I 2 5 The carpeting was added to 4000 parts of water con- H taining the aforementioned sulfobetaine 1 part the tetrasodium salt of ethylenediamine tetraacetic acid 0.25 part tetrasodium pyrophosphate 0.2 part.

b. The procedure described in (a) above was repeated, except that N-ethyl-N-phenyl-N,N- I v The dyebath was adjusted to pH 6 with monosodium diethylethylenediamine was replaced with an equivaphosphate and the temperature raised to F. for 10 minutes. 0.05 Part of the dye of Example 1 was added and, after holding the dyebath of 80F. for l rninutes the temperature was raised at ca. 2F. per minute to 210F. and held at this temperature for l hour. The car peting was rinsed in cold water anddried. Theaci d modified band was dyed a scarlet shade. The unmodified' fibers had a negligible stain. I

EXAMPLE 18 Printing of BCF Nylon Styling Carpeting A sample of BCF nylon styling carpeting was printed with a mixture containing 15 the cationic dye of Example 3 5 parts the sulfobetaine described in Example l7 0.5 part glacial acetic acid 5 parts carrageenin-thickener to give the desired viscosity water to 100 parts The carpeting was steamed at 2l2220F. for 10 minutes rinsed, scoured for minutes at 160F. in a 0.03% aqueous solution of the condensationproduct of moles of ethylene oxide with 1 mole of C alcohol, rinsed and dried. The acid-modified nylon fibers were dyed a scarlet shade. The unmodified fibers had a negligible stain.

EXAMPLE 19 Continuous Dyeing of Nylon Styling Carpeting Using Kusters Equipment as described in Textile Chemist and Colorist, Jan. 14, 1970, pages 6l2, nylon styling carpeting as described in Example 18 above was run 7 through a wet-out bath at 80F containing an organic alcohol extended with ethylene oxide 1.5 g/l a sulfated polyglycol ether 0.6 g/l Pickup was about 80%. The carpeting was then continuously treated with an aqueousdyebath composition containing the dye of Example 2 5 g/l an organic alcohol extended with ethylene oxide 0.25 g/l a sulfated polyglycol ether 1.25 g/l 40 a purified natural gum ether 2 g]! the sulfobetaine described in Example l7" 5 g/l acetic acid I 3 monosodium phosphate to adjust the pH to ca. 5

The dyebath temperature was 80F.- Pickup was about 200%. The carpeting was then run through a steamer at 212F. in which the dwell time was 8 minutes. The carpeting was rinsed thoroughly and dried. The acid-modified nylon fibers were dyed an orange shade; the unmodified fibers were negligibly stained.

EXAMPLE 20 Evaluation of Cross-Staining and Light-Fastness The results appear in Table 4. In each case, the shade depth on the acid-modified skein was adjusted to be visually equal to that of the monocationic dye at 0.5% (on the weight of the fiber).

Ratings of staining and light-fastness were made according to the Gray Scale, as given in the Manual of the American Association of Textile Chemists and Color- .ists. The numbers have the following significance:

W weak Table 4 Stain on un- Light-Fastness modified on Acid-Modified Light- Nylon hours Dyeable" v Xenon Arc Example Shade Nylon Fade-Ometer Commercial dye red 32' 5-4W red 5-4 2 orange 4-3 i 3 scarlet 5 5-4W 4 scarlet 5 5-4W 5 scarlet 5 54W 6 orange 43 7 yellow v v 5 4 9(a) maroon 4 9(b) violet 5 9(c) maroon 5-4 4-3W l0 maroon 5-4 4W l2 orange 5-4 5-4W l3 scarlet 54 1 5-4W l4 maroon 5-4 54W l5 orange 5 5-4W l6(a) violet 4 32-Y,W l6( b) blue-violet 4 4W, 3R

The embodiments of the invention in which an exclu sive property or privilege is claimed are defined as follows: l

1. In a process for dyeing nylon styling yarns comprising contacting "said' yarns with a dye dispersed in an aqueous dyebath having apl-l of from 3 to 9 and a temperature of about from 70 to C. and containing about from 0.05 to 0.5% based on the weight of the yarn of a dyeing assistant, the improvement comprising using a biscationic azo dye having the formula:

R is alkyl or hydroxyalkyl R is alkyl; hydroxyalkyl or banzyl Xv alkyl i alkyl or R and R together is piperidiniiim or pyrrolidinium or R R and R together is pyridinium R, is H or Cl W is 1,4-naphthylene or 8 R and R is H, alkyl, alkoxy or .Cl

R is H, alkyl, alkoxy, Cl NHCO alkyl or NHCOC H R is H, Cl, alkyl or alkoxy al-kyl and where each alkyl, alkoxy and hydroxyalkyl contains l to 4 carbon atoms; at a pH of from 6 to 6.5.

2. The improved process of claim 1 wherein R is CH R is CH R is CH R is H, m is 0, R is CH R is H and UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,904, 358

DATED September 9, 1975 INVENTOR(S) Daniel Shaw James It is certified that error appears in the ab0veidentitied patent and that said Letters Patent are hereby corrected as shown below:

On the title page, the date of issue should read September 9, 1975--a Column 25, line 13, a comma should be inserted between "Cl" and "NHCO" Column 26, line 6, the equal signs should be changed to is-.

Column 26, line 17, the formula should read:

X N Z S CH (|IH CH N (CH Signed and Sealed this ninth Day Of March 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks 

1. IN A PROCESS FOR DYEING NYLON STYLING YARNS COMPRISING CONTACTING SAID YARNS WITH A DYE DISPERSED IN AN AQUEOUS DYEBATH HAVING A PH OF FROM 3 TO 9 AND A TEMPERATURE OF ABOUT FROM 70* TO 100*C. AND CONTAINING ABOUT FROM 0.05 TO 0.5% BASED ON THE WEIGHT OF THE YARN OF A DYEING ASSISTANT, THE IMPROVEMENT COMPRISING USING A BISCATIONIC AZO DYE HAVING THE FORMULA:
 2. The improved process of claim 1 wherein R1 is CH3, R2 is CH3, R3 is CH3, R4 is H, m is 0, R7 is CH3, R8 is H and 